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| United States Patent |
5,206,209
|
|
Minami
, et al.
|
April 27, 1993
|
Heat-sensitive recording sheet
Abstract
A heat-sensitive recording sheet of this invention comprises in a
heat-sensitive color-developing layer both
bis(4-hydroxyphenyl)butylacetate as an organic color-developing agent and
a particular fluorane-leuco dye. This sheet provides an intense clear
image less discoloration and superior heat-resistant preservability.
| Inventors:
|
Minami; Toshiaki (Tokyo, JP);
Fukuchi; Tadakazu (Tokyo, JP);
Kaneko; Toshio (Tokyo, JP)
|
| Assignee:
|
Jujo Paper Co., Ltd. (Tokyo, JP)
|
| Appl. No.:
|
683548 |
| Filed:
|
April 10, 1991 |
Foreign Application Priority Data
| Current U.S. Class: |
503/209; 427/150; 427/151; 503/216; 503/217; 503/221; 503/226 |
| Intern'l Class: |
B41M 005/30 |
| Field of Search: |
427/150-152
503/209,216,217,221,225
|
References Cited
U.S. Patent Documents
| 4977132 | Dec., 1990 | Tsuchida et al. | 503/220.
|
Primary Examiner: Hess; B. Hamilton
Attorney, Agent or Firm: Sherman and Shalloway
Claims
We claim:
1. A heat-sensitive recording sheet comprising a support having thereon a
color-developing layer which comprises as main ingredients a colorless or
pale colored basic chromogenic dye and an organic color-developing agent,
wherein said color-developing layer comprises both
bis(4-hydroxyphenyl)butylacetate as an organic color-developing agent and
at least one fluorane-leuco dye selected from dyes represented by the
following formulae (I), (II), (III) and (IV) as a colorless or pale
colored basic chromogenic dye:
##STR2##
2. The heat-sensitive recording sheet according to claim 1, wherein said
color-developing layer comprises 1-8 parts by weight of said organic
color-developing agent and 1-20 parts by weight of filler, based on 1 part
by weight of said colorless basic chromogenic dye, and 10-25% by weight of
binder in total solid content.
3. The heat sensitive recording sheet according to claim 1, wherein said
color-developing layer further comprises a stabilizer.
4. The heat-sensitive recording sheet according to claim 3, wherein said
stabilizer is at least one material selected from the group consisting of
metal salts of p-nitrobenzoic acid and metal salts of phthalic acid
monobenzylester.
5. The heat-sensitive recording sheet according to claim 1, wherein said
color-developing layer further comprises fluorane-leuco dyes other than
said fluorane-leuco dyes represented by the formulae (I), (II), (III), and
(IV).
6. The heat-sensitive recording sheet according to claim 1, wherein said
support is at least one member selected from the group consisting of paper
and plastic.
7. The heat-sensitive recording sheet according to claim 6, wherein said
paper is a synthetic paper.
8. The heat-sensitive recording sheet according to claim 1, wherein an
over-coat layer is formed on said color-developing layer.
9. The heat-sensitive recording sheet according to claim 1, wherein an
under-coat layer is formed under said color-forming layer.
10. The heat-sensitive recording sheet according to claim 1, wherein said
support is a film.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a heat-sensitive recording sheet which is
superior in the heat resistance of the background, and the water
resistance, oil resistance and heat resistance of image.
2. Prior Art
In general, a heat-sensitive recording sheet is produced by applying on a
support, such as paper, synthetic paper, film, plastic, etc., a coating
material which is prepared by individually grinding and dispersing a
colorless chromogenic dye and an organic color-developing agent, such as
phenolic material, etc., into fine particles, mixing the resultant
dispersions with each other and then adding thereto binder, filler,
sensitizer, slipping agent and other auxiliaries. The coating, when heated
by thermal pen, thermal head, hot stamp, laser beam, etc., undergoes
instantaneously a chemical reaction which forms a color. These
heat-sensitive recording sheets have now been finding a wide range of
applications, including industrial measurement recording instruments,
terminal printers of computer, facsimile equipment, automatic ticket
vending machines, printer for bar-code-label, and so on. In recent years,
as the application of such recording is diversified and the performance of
such recording equipment is enhanced, high qualities are required for
heat-sensitive recording sheets. For example, even with small heat energy
in a high speed recording, both the clear image with a high density and
the better preservability such as better resistance to light, weather and
oil, etc. are required. The conventional heat-sensitive recording sheets
are disclosed, for examples, in the Japanese Patent Publication Nos.
43-4160 and 45-14039.
However, these heat-sensitive recording sheets have as a defect, for
example, an insufficient image density in high speed recording owing to
the inferior thermal responsibility.
As the methods for improving the above defect, there have been developed
the high sensitive dyes, for example,
3-N-methyl-N-cyclohexylamio-6-methyl-7-anilinofluorane (in the Japanese
Patent Laid-Open No. 49-109120) and
3dibutylamino-6-methyl-7-anilinofluorane (in the Japanese Patent Laid Open
No. 59-190891) as leuco dye. Further, there have been proposed the
color-developing agents of superior color-formation, for example,
1,7-bis(4-hydroxyphenylthio)-3,5-dioxaheptane (in the Japanese Patent
Laid-Open 59-106456), 1,5-bis(4-hydroxyphenylthio)-3-oxaheptane (in the
Japanese Patent Laid-Open No. 59-116262) and
4-hydroxy-4'-isopropoxydiphenylsulfone (in the Japanese Patent Publication
No. 63-46067). Using these chemicals, the technologies for the recording
with high speed and sensitivity have been disclosed.
Although these heat-sensitive recording sheets provide a high sensitivity,
they have a problem in an inferior heat-resistance, i.e. a formation of
background fogging in the high temperature storage.
Further, they exhibit the extremely inferior preservability of the recorded
image, which causes the following defects. In the adhesion to moisture or
serum, or in the contact with plasticizer (DOP, DOA, etc.) in a wrapping
film, the image density is prominently decreased or the recorded image
disappears.
Further, Japanese Patent Application No. 1-267590 discloses a technique
providing a heat-sensitive recording sheet which is superior in heat
resistance, water resistance and oil resistance. In this case, however,
there are problems in that a heat-recording sheet is inferior in
preservability(heat-, water-, and oil-resistance), somewhat insufficient
dynamic image density and causes slight formation of background fogging.
SUMMARY OF THE INVENTION
It is the object of this invention to provide a heat-sensitive recording
sheet which has a sufficient dynamic image density, and which is superior
in preservability (heat-, water-, and oil-resistance) and causes no
formation of background fogging.
The above object can be performed as follows. The heat-sensitive recording
sheet comprises a support having thereon a color-developing layer which
comprises both bis-(4-hydroxyphenyl)-butylacetate, a particular diphenol
compound, as an organic color-developing agent and at least one
fluoraneleuco dye selected from
3-n-dipentylamino-6-methyl-7-anilinofluorane represented by the following
formula (I), 2-(4-oxa-hexyl)-3-dimethylamino-6-methyl-7-anilinofluorane
represented by the following formula (II),
2-(4-oxa-hexyl)-3-diethylamino-6-methyl-7-anilinofluorane represented by
the following formula (III) and
2-(4-oxa-hexyl)-3-dipropylamino-6-methyl-7-anilinofluorane represented by
the following formula (IV).
##STR1##
DETAILED DESCRIPTION OF THE INVENTION
The fluorane-leuco dye of this invention can be used in combination with
other fluorane-leuco dyes in such a range that the effects of this
invention is not deteriorated. Typical examples for these fluorane-leuco
dyes include: 3-diethylamino-6-methyl-7-anilinofluorane,
3-(N-ethyl-P-toluidino)-6-methyl-7-anilinofluorane,
3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane,
3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane,
3-pyrolidino-6-methyl-7-anilinofluorane,
3-piperidino-6-methyl-7-anilinofluorane,
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane,
3-diethylamino-7-(m-trifluoromethylanilino)fluorane,
3-dibuthylamino-6-methyl-7-anilinofluorane,
3-diethylamino-6-chlor-7-anilinofluorane,
3-dibutylamino-7-(o-chloranilino) fluorane and
3-diethylamino-7-(o-chloranilino) fluorane.
As in the dye of this invention, the color-developing agent of this
invention can be used in combination with the other color-developing
agents in such a range that the effects are not deteriorated.
As sensitizers, there can be used fatty acid amide such as stearic acid
amide, palmitic acid amide; ethylenebis amide; montan wax; polyethylene
wax; dibenzyl terephthalate; benzyl p-benzyloxybenzoate;
d-p-tolylcarbonate; p-benzylbiphenyl, phenyl .alpha.-naphthylcarbonate;
1,4-diethoxynaphthalene; 1-hydroxy-2-naphthoic acid phenyl ester;
1,2-di(3-methylphenoxy) ethane; di(p-methylbenzyl) oxalate;
.beta.-benzyloxynaphthalene; 4-biphenyl-p-tolylether; and the like.
As the binders of this invention, there can be mentioned, for example, a
fully saponified polyvinyl alcohol having a polymerization degree of 200
-1900, a partially saponified polyvinyl alcohol, carboxylated polyvinyl
alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified
polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified
polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl
cellulose, styrene/maleic acid anhydride copolymers, styrene/butadiene
copolymers, cellulose derivatives such as ethyl cellulose, acetyl
cellulose, etc.; polyvinyl chloride, polyvinyl acetate, polyacryl amide,
polyacrylic acid ester, polyvinyl butyral, polystyrol and copolymers
thereof; polyamide resin, silicone resin, petroleum resin, terpene resin,
ketone resin and cumaron resin.
These polymeric materials may be used after they were dissolved in an
solvent such as water, alcohol, ketone, ester, hydrocarbon, etc., or after
they were emulsified or dispersed in water or a solvent other than water.
These binders can be used in combination depending upon the required
quality.
Further, metal salts of p-nitrobenzoic acid (Ca-and Zn-salts) or metal
salts of phthalic acid monobenzylester (Ca- and Zn-salts) as known
stabilizers can be added thereto.
The filler used in this invention includes organic and inorganic fillers.
Typical examples for fillers include silica, calcium carbonate, kaolin,
calcined kaolin, diatomaceous earth, talc, titanium dioxide and aluminum
hydroxide.
Furthermore, the following additives can be used: releasing agent such as
fatty acid metal salts, slipping agent such as waxes, UV-absorbers of
benzophenone type or triazole type, water resistance agent such as
glyoxal, dispersants, antifoamers and the like.
The species and the amount of organic color-developing agent, colorless
basic chromogenic dye and other ingredients, which are used in this
invention, are determined depending upon the performance and recording
aptitude required for the recording sheet, and are not otherwise limited.
However, in ordinary cases, it is suitable to use 1-8 parts by weight of
organic color-developing agent, 1-20 parts by weight of filler, based on 1
part by weight of colorless basic chromogenic dye, and to add 10-25% by
weight of a binder in total solid content.
The aimed heat-sensitive recording sheet may be obtained by coating the
above coating material on a substrate such as paper, synthetic paper,
film, plastic, etc.
For improving the preservability, further, an over-coat layer of a polymer,
etc. containing a filler is formed on the color-developing layer.
For improving the preservability and sensitivity, an undercoat layer
containing an organic or inorganic filler is formed under the
color-developing layer.
The above organic color-developing agent, the above colorless basic
chromogenic dye, and if necessary, other ingredients are ground to a
particle size of several microns or smaller by means of a grinder or
emulsifier such as a ball mill, attritor, sand grinder, etc., and binders
and various additives in accordance with the purpose, are added thereto to
prepare a coating material.
The reason for providing the effects of this invention in the combined use
of a particular color-developing agent and a particular dye is thought as
follows.
The reason for the superior dynamic image density is due to the fact that
the dye has a high melting, dissolving and diffusion speed, as well as a
great saturation solubility into the color-developing agent of this
invention to thereby form a recorded image instantaneously on contact with
thermal heads of high temperature.
The reason why the recorded image is superior in water resistance and oil
resistance is explained as follows. Generally, a heat-sensitive recording
sheet is composed of a colorless basic dye as an electron donor and of an
organic acidic material, such as phenolic material, aromatic carboxylic
acid, organic sulfonic acid, etc. as an electron acceptor. The heat-melt
reaction between the colorless basic dye and the color-developing agent is
an acid-base reaction based on the donating-acceptance of electrons,
whereby a pseudo-stable "electron charge transfer complex" is produced,
which forms a color.
In the use of bis(4-hydroxyphenyl)butylacetate as an organic
color-developing agent, the chemical binding force in color-forming
reaction between bis(4-hydroxyphenyl)butylacetate and a particular
fluorane-leuco dye as a colorless basic dye is prominently strong, in
comparison with that in color-forming reaction between a fluorane-leuco
dye and a color-developing agent other than that of this invention.
The color-developing agent other than that of this invention includes, for
example, 4-hydroxy benzoic acid benzyl ester,
4-hydrxy-4'-isopropoxydiphenylsulfone,
1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane and
4,4'-dihydroxydiphenylsulfone. Owing to the strong chemical binding force,
the chemical bonding do not deteriorate for a long period even under the
circumstance of heat, water, oil, etc., so that a record image is stable.
EXAMPLES
The following examples illustrate this invention, although this invention
is not limited to examples. The parts are parts by weight.
EXAMPLE 1 (Test Nos. 1-3)
______________________________________
Liquid A (dispersion of dye)
Dye (see Table 1) 2.0 parts
10% aqueous solution of polyvinyl alcohol
4.6 parts
Water 2.5 parts
Liquid B (dispersion of color-developing agent)
bis(4-hydroxyphenyl)butylacetate
6.0 parts
10% aqueous solution of polyvinyl alcohol
18.8 parts
Water 11.2 parts
______________________________________
Each liquid of the above composition was ground to an average particle size
of 1 micron by a sand grinder. Then, the dispersions were mixed in the
following proportion to prepare a coating material.
______________________________________
Coating material
______________________________________
Liquid A (dispersion of dye)
9.1 parts
Liquid B (dispersion of color-developing agent)
36.0 parts
Kaolin clay (50% aqueous dispersion)
12.0 parts
______________________________________
The coating material was applied on one side of a base paper weighing 50
g/m.sup.2 in a coating weight of 5.0 g/m.sup.2 and then dried. The
resultant paper was treated to a smoothness of 400-500 seconds by a
supercalender. In this manner, a heat-sensitive recording sheet was
obtained.
Comparative Example 1-2
A heat-sensitive recording sheet was obtained in the same manner as in
Example 1 except that the dye in Table 1 is used instead of the dye of
Liquid A.
Comparative Example 3-6
______________________________________
Liquid C (dispersion of dye)
Dye (see Table 1) 2.0 parts
10% aqueous solution of polyvinyl alcohol
4.6 parts
Water 2.5 parts
Liquid D (dispersion of color-developing agent)
Color-developing agent (see Table 1)
6.0 parts
10% aqueous solution of polyvinyl alcohol
18.8 parts
Water 11.2 parts
______________________________________
Each liquid of the above composition was ground to an average particle size
of 1 micron by a sand grinder. Then, the dispersions were mixed in the
following proportion to prepare a coating material.
______________________________________
Coating material
______________________________________
Liquid C (dispersion of dye)
9.1 parts
Liquid D (dispersion of color-developing agent)
36.0 parts
Kaolin clay (50% aqueous dispersion)
12.0 parts
______________________________________
The coating material was applied on one side of a base paper weighing 50
g/m.sup.2 in a coating weight of 5.0 g/m.sup.2 and then dried. The
resultant paper was treated to a smoothness of 400-500 seconds by a
supercalender. In this manner, a black color-forming heat-sensitive
recording sheet was obtained.
EXAMPLES 5-6
______________________________________
Liquid A (dispersion of dye)
Dye (see Table 2) 2.0 parts
10% aqueous solution of polyvinyl alcohol
4.6 parts
Water 2.5 parts
Liquid B (dispersion of color-developing agent)
Bis(4-hydroxphenyl)butylacetate
6.0 parts
10% aqueous solution of polyvinyl alcohol
18.8 parts
Water 11.2 parts
______________________________________
Each liquid of the above composition was ground to an average particle size
of 1 micron by a sand grinder. Then, the dispersions were mixed in the
following proportion to prepare a coating material.
______________________________________
Coating material
______________________________________
Liquid A (dispersion of dye)
9.1 parts
Liquid B (dispersion of color-developing agent)
36.0 parts
Kaolin clay (50% aqueous dispersion)
12.0 parts
______________________________________
The coating material was applied on one side of a base paper weighing 50
g/m.sup.2 in a coating weight of 5.0 g/m.sup.2 and then dried. The
resultant paper was treated to a smoothness of 400-500 seconds by a
supercalender. In this manner, a black color-forming heat-sensitive
recording sheet was obtained.
Comparative Examples 7-8
______________________________________
Liquid A (dispersion of dye)
Dye (see Table 2) 2.0 parts
10% aqueous solution of polyvinyl alcohol
4.6 parts
Water 2.5 parts
Liquid E (dispersion of color-developing agent)
4-Hydroxy-4'-n-propoxydiphenylsulfone
6.0 parts
10% aqueous solution of polyvinyl alcohol
18.8 parts
Water 11.2 parts
______________________________________
Each liquid of the above composition was ground to an average particle size
of 1 micron by a sand grinder. Then, the dispersions were mixed in the
following proportion to prepare a coating material.
______________________________________
Coating material
______________________________________
Liquid A (dispersion of dye)
9.1 parts
Liquid E (dispersion of color-developing agent)
36.0 parts
Kaolin clay (50% aqueous dispersion)
12 parts
______________________________________
The coating material was applied on one side of a base paper weighing 50
g/m.sup.2 in a coating weight of 5.0 g/m.sup.2 and then dried. The
resultant paper was treated to a smoothness of 400-500 seconds by a
supercalender. In this manner, a black color-forming heat-sensitive
recording sheet was obtained.
The heat-sensitive recording sheets obtained by the above Example and
Comparative Examples were tested for their qualities and performances. The
test results are summarized in Tables 1 and 2.
Notes
(1) Dynamic image density:
A heat-sensitive recording sheet is recorded with an impressed voltage of
18.03 volts and a pulse width of 3.2 milli-seconds by using the thermal
facimile KB-4800 manufactured by TOSHIBA CORPORATION, and the optical
density of the recorded image is measured by a Macbeth densitometer
(RD-914, using amber filter which is employed in other samples).
(2) Heat resistance:
A heat-sensitive sheet before the recording allows to stand for 24 hours at
60.degree. C., and the image density is measured by a Macbeth
densitometer.
(3) Water-resistance:
The heat-sensitive recording sheet recorded in Note (1) is dipped in water
at 20.degree. C. for 24 hours. After drying, the recorded image is
measured by a Macbeth densitometer. Residual rate is calculated from the
following equation.
##EQU1##
(4) Oil-resistance:
The image density obtained in Note (1) is defined as image density before
oil treatment. A drop of salad oil is applied on the recorded image, and
wished off with a filter paper after 10 secs. The obtained paper allows to
stand for 1 hour at room temperature. Residual rate is calculated from the
following equation.
##EQU2##
(5) Heat-resistant preservability:
The heat-sensitive recording sheet recorded in Note (1) allows to stand for
24 hours at 60.degree. C., and the recorded density is measured by a
Macbeth densistometer.
Residual rate is calculated from the following equation.
##EQU3##
TABLE 1
__________________________________________________________________________
Test Results
__________________________________________________________________________
(2)
Heat
(1) resistance
Dynamic
Before
After
Color-developing image
treat-
treat-
agent Dye density
ment
ment
__________________________________________________________________________
Example
1 Bis(4-hydroxyphenyl)butyl-
3-n-Dipentylamino-
1.32 0.05
0.07
acetate 6-methyl-7-anilinofluorane
2 Bis(4-hydroxyphenyl)butyl-
2-(4-Oxa-hexyl)-3-
1.30 0.05
0.07
acetate dimethylamino-6-methyl-
7-anilinofluorane
3 Bis(4-hydroxyphenyl)butyl-
2-(4-Oxa-hexyl)-3-
1.31 0.05
0.08
acetate diethylamino-6-methyl-
7-anilinofluorane
4 Bis(4-hydroxyphenyl)butyl-
2-(4-Oxa-hexyl)-3-
1.29 0.05
0.07
acetate dimethylamino-6-methyl-
7-anilinofluorane
Comparative
Example
1 Bis(4-hydroxyphenyl)butyl-
3-(N-Cyclohexyl-N-
1.21 0.06
0.11
acetate methylamino)-6-methyl-
7-anilinofluorane
2 Bis(4-hydroxyphenyl)butyl-
3-Dibutylamino-6-methyl-
1.24 0.06
0.09
acetate 7-anilinofluorane
3 4-Hydroxy benzoic
3-n-Dipentylamino-6-
1.30 0.06
0.13
acid benzyl ester
methyl-7-anilinofluorane
4 4-Hydroxy-4'- 3-n-Dipentylamino-6-
1.29 0.06
0.10
isopropoxydiphenyl sulfone
methyl-7-anilinofluorane
5 1,7-Di(4-hydroxy-
2-(4-Oxa-hexyl)-3-
1.30 0.06
0.12
phenylthio)-3,5-
dimethylamino-6-methyl-
dioxaheptane 7-anilinofluorane
6 4,4'-Dihydroxy-
2-(4-Oxa-hexyl)-3-
1.00 0.07
0.14
diphenylsulfone
diethylamino-6-methyl-
7-anilinofluorane
__________________________________________________________________________
(3) (4)
Water Oil
resistance resistance
Before
After
Residual
Before
After
Residual
treat-
treat-
rate treat-
treat-
rate
ment
ment
(%) ment
ment
(%)
__________________________________________________________________________
Example
1 1.32
1.18
89 1.32
1.21
92
2 1.30
1.19
92 1.30
1.18
91
3 1.31
1.20
92 1.31
1.21
92
4 1.29
1.16
90 1.29
1.18
91
Comparative
Example
1 1.21
0.95
79 1.21
0.97
80
2 1.24
0.98
79 1.24
0.96
77
3 1.30
1.01
78 1.30
0.84
65
4 1.29
1.04
81 1.29
1.06
82
5 1.30
1.04
80 1.30
0.94
72
6 1.00
0.60
61 1.00
0.77
77
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
Heat-resistant
preservability
Before
After
Color-developing treat-
treat-
Residual
agent Dye ment
ment rate(%)
__________________________________________________________________________
Example
Bis(4-hydroxy-
3-n-Dipentyl-
1.32
1.28 97
5 phenyl)butyl-
amino-6-methyl-
acetate 7-anilinofluorane
Example
Bis(4-hydroxy-
2-(4-Oxa-hexyl)-
1.30
1.26 97
6 phenyl)butyl-
3-dimethylamino-
acetate 6-methyl-7-
anlinofluorane
Compar-
4-Hydroxy-
3-n-Dipentyl-
1.31
0.98 75
ative 4'-n-pro-
amino-6-methyl-
Example
poxydiphenyl-
7-anilinofluorane
7 sulfone
Compar-
4-Hydroxy-
2-(4-Oxa-hexyl)-
1.30
0.99 76
ative 4'-n-pro-
3-dimethylamino-
Example
poxydiphenyl-
6-methyl-7-
8 sulfone anilinofluorane
__________________________________________________________________________
The advantageous features of the heat-sensitive recording sheets obtained
by this invention are as follows:
(1) An intense, clear image in high-speed and high-density recording owing
to excellent thermal responsibility,
(2) Less discoloration of the recorded image on contact with plasticizer,
(3) Less discoloration of the recorded image on contact with moisture,
(4) Stable brightness under the condition of high temperature,
(5) Stable image under the condition of high temperature (superior
heat-resistant preservability)
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